Russian Chemical Bulletin, International Edition, Vol. 63, No. 12, pp. 2647—2651, December, 2014
2647
Regularities of glycidol synthesis by the liquidꢀphase epoxidation
of allyl alcohol with hydrogen peroxide
A. V. Sulimov,а S. M. Danov,а A. V. Ovcharova,а A. A. Ovcharov,а and V. R. Flidb
aR. E. Alekseev Nizhny Novgorod State Technical University,
24 ul. Minina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831) 436 9475. Eꢀmail: epoxide@mail.ru
bM. V. Lomonosov Moscow State University of Fine Chemical Technology,
86 prosp. Vernadskogo, 119571 Moscow, Russian Federation
The main features of the liquidꢀphase epoxidation of allyl alcohol by hydrogen peroxide in
an organic solvent in the presence of the titaniumꢀcontaining zeolite in the batch reactor were
studied. The influence of the amount of the solvent, ratio of reactants, and temperature on the
rate of glycidol synthesis was revealed.
Key words: glycidol, allyl alcohol, hydrogen peroxide, epoxidation, titaniumꢀcontaining
zeolite TSꢀ1.
the suspension was washed with water to рН 7—8, dried for 12 h
at 120 С in vacuo (20 Torr), and calcined in a muffle furnace at
550 С for 6 h.
Glycidol is a valuable intermediate in the production
of synthetic glycerol and its derivatives, as well as surfacꢀ
tants, plasticizers, textile dyes, photochemicals, drugs,
pesticides, a series of rubbers, varnishes, and thermoꢀ
reactive resins and plastics.1
Several methods of glycidol synthesis are known, in
particular, dehydrohalogenation of glycerol monochloroꢀ
hydrin,2,3 hydrolysis of epichlorohydrin, and the reaction
of allyl alcohol with perbenzoic acid.4,5 The primary disꢀ
advantages for these methods are many byꢀproducts, high
expenses of energy sources, and hardly utilized effluents.
Ecological and economical requirements dictate the neꢀ
cessity to develop a novel, environmentally friendly, and
alternative technology of glycidol synthesis.
One of the most promising methods for glycidol synꢀ
thesis is the liquidꢀphase epoxidation of allyl alcohol by an
ecologically safe oxidant, hydrogen peroxide, in the presꢀ
ence of synthetic titaniumꢀcontaining zeolites.6 The main
objective of this work was to investigate the influence of
the amount of solvent, reaction temperature, and reactant
ratio on the liquidꢀphase oxidation of allyl alcohol by an
aqueous solution of hydrogen peroxide on titaniumꢀconꢀ
taining zeolite.
The specific surface, total pore volume, and poreꢀsize disꢀ
tribution were measured on a TriStar 3020 automated gas adꢀ
sorption analyzer (Micromeritics). Using the data obtained, the
following parameters of the porous catalyst structure were calcuꢀ
lated in the automatic mode: specific surface 316.66 m2 g–1, and
pore volume 0.182 cm3 g–1 with most of the pores being in the
range from 32 to 45 Å. The Ti content based on TiO2 is 3.16 wt.%,
and the Si/Ti molar ratio is 25.
The epoxidation of allyl alcohol was studied in a laboratory
batch reactor equipped with an electromagnetic stirrer and a
system of constant temperature maintenance. The calculated
amounts of allyl alcohol, solvent, and catalyst were loaded into
the reactor. Then the magnetic stirrer drive was connected to
the thermostat, and the temperature of the reactor was mainꢀ
tained at a specified temperature for 10—15 min. Then the reacꢀ
tor was loaded with hydrogen peroxide, and the time of experiꢀ
ment onset was detected. Sampling for analysis was performed
with a capillary at certain time intervals.
The composition of the reaction mixture was determined by
gas chromatography on a Khromos GKhꢀ1000 instrument
equipped with a flameꢀionization detector with a metallic colꢀ
umn (2 m 3 mm) packed with a ChromatonꢀNꢀAW support
with the Carbowax 6000 chromatographic phase in an amount of
15% of the support weight. Nitrogen was used as a carrier gas at
flow rate of 50 mL min–1. The temperatures of the evaporaꢀ
tor and the thermostat of the columns were maintained at
180 and 130 С, respectively. The temperature of the detector
was 200 С. The composition of the reaction mixture was deterꢀ
mined by the absolute calibration method, and the amount
of hydrogen peroxide was determined by iodometric titration.
The procedures used were evaluated averaging results of 5—7 parꢀ
allel experiments, and their rootꢀmeanꢀsquare error did not
exceed 5%. The initial reaction rate of the process was calcuꢀ
Experimental
Methanol and glycidol (TU 6ꢀ09ꢀ14ꢀ2635ꢀ79) (both highꢀ
purity grade), 33—34% hydrogen peroxide (specialꢀpurity grade,
TU 2611ꢀ069ꢀ05807977ꢀ2006), and allyl alcohol (TU 6ꢀ01ꢀ753ꢀ77)
were used. The catalyst (titaniumꢀcontaining zeolite) was preꢀ
pared using a known procedure.7
The catalyst was synthesized in an autoclave at 170 С for
40 h with stirring. The solid precipitate formed after cooling of
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2647—2651, December, 2014.
1066ꢀ5285/14/6312ꢀ2647 © 2014 Springer Science+Business Media, Inc.